WO2022154097A1

WO2022154097A1 - Organic material liquid dehydration method

Info

Publication number: WO2022154097A1
Application number: PCT/JP2022/001207
Authority: WO
Inventors: 剛裕大崎; 雄治片山; 諒一高田; 慶太郎鈴村
Original assignee: 旭化成株式会社
Priority date: 2021-01-15
Filing date: 2022-01-14
Publication date: 2022-07-21
Also published as: CN116710191A; JPWO2022154097A1; JP7481508B2; EP4279166A1

Abstract

Provided is a method for processing a material liquid, which is an organic solution containing a small amount of water, using forward osmosis under a non-heated condition to obtain a dehydrated material liquid without causing degradation or change in quality of a solute. This method is for dehydrating a material liquid containing a first organic solvent, water, and a first solute, and comprises a dehydration step for bring the material liquid and an induction organic liquid containing a second organic solvent into contact with each other through a forward osmosis membrane to obtain a dehydrated material liquid that has the moisture content thereof reduced to less than 1 mass% through dehydration. In one mode, the initial moisture content of the material liquid in the dehydration step is not less than 1 mass% but less than 30 mass%, and the initial moisture content of the induction organic liquid is less than the initial moisture content of the material liquid.

Description

Dehydration method of organic raw material liquid

The present invention relates to a method for dehydrating an organic raw material liquid. More specifically, the present invention relates to a method of dehydrating water from a raw material liquid containing an organic solvent, a small amount of water, and a solute by a forward osmosis method.

In various chemical processes, there is a dehydration step that removes water contained in the organic liquid. For example, when dehydrating from a raw material solution before a chemical reaction called a water-free reaction in which the desired reaction does not proceed in the presence of water, in order to recrystallize the solute to obtain crystals of the desired shape, size or purity. When adjusting the amount of water in the organic solution, water produced as a by-product during the equilibrium reaction may be removed from the reaction system to improve the yield of the target product.

As a general dehydration method, an azeotropic evaporation method in which water and the added organic solvent are removed by adding an organic solvent for forming an azeotropic mixture with water to the raw material liquid and heating the raw material liquid, and water are used. A method of adding a desiccant that selectively adsorbs to a raw material solution is known.

However, the azeotropic evaporation method has problems such as the quality of the components in the raw material liquid changing due to heating. In the method of adding the desiccant to the raw material liquid, there is a concern that the solute in the raw material liquid is also adsorbed and that it takes time to remove the added desiccant from the raw material liquid before the next step. Further, when the scale of the dehydration process is increased, there is a problem that it is difficult to obtain the reproducibility of dehydration.

Therefore, as another useful dehydration method, a forward osmosis (FO: Forward Osmosis) method is known in which the solvent in the raw material liquid is separated by utilizing the difference in osmotic pressure. In the forward osmosis method, the raw material liquid and the inductive liquid having a higher osmotic pressure than the raw material liquid are brought into contact with each other through a forward osmosis (FO) membrane, and the solvent is transferred from the raw material liquid to the inductive liquid to move the raw material liquid. Is a method of concentrating. When the solvent is water, the aqueous solution can be dehydrated and concentrated using the forward osmosis method. The forward osmosis method does not require heating and pressurization. Therefore, it is expected that the forward osmosis method can prevent the decomposition or alteration of the solute and can process the solution while maintaining the quality of the solute.

For example, Patent Document 1 describes a method of dehydrating an aqueous alcohol solution by a forward osmosis method. Further, Patent Document 2 describes a system for treating a solution containing an organic compound using a forward osmosis membrane using a polyketone as a membrane material, and a method for removing water from a hydrous substance using this system. ing.

International Publication No. 2010/080208 International Publication No. 2016/024573

However, the techniques described in Patent Document 1 and Patent Document 2 have not been able to remove a small amount of water contained in the organic solution. In view of the above circumstances, one aspect of the present invention provides a method for dehydrating the raw material liquid without decomposing or deteriorating the solute contained in the raw material liquid which is an organic solution containing a small amount of water.

That is, an example of the embodiment of the present invention is as shown below.
[1] A method for dehydrating a raw material liquid containing a first organic solvent, water and a first solute.
A dehydration step of bringing the raw material liquid and an induced organic liquid containing a second organic solvent into contact with each other via a forward osmosis membrane to obtain a dehydrated raw material liquid dehydrated to a water content of less than 1% by mass is included.
Here, the initial water content of the raw material liquid in the dehydration step is 1% by mass or more and less than 30% by mass, and the initial water content of the induced organic liquid is smaller than the initial water content of the raw material liquid. Method.
[2] The forward osmosis membrane is a composite membrane composed of a separation active layer and a microporous support membrane.
The difference ΔHSP of the solubility parameter between the induced organic liquid and the separated active layer is ΔHSP <16 (MPa) ^0.5 , and the saturated water content of the induced organic liquid is 0.5% by mass or more.
The method according to the above aspect 1.
[3] The solubility parameter of the derived organic liquid is 13 (MPa) ^0.5 ≤ δd ≤ 20 (MPa) ^0.5 , 2 (MPa) ^0.5 ≤ δp ≤ 18 (MPa) ^0.5 , 2 (MPa) ^0.5 ≤ δH ≤ 28 ( MPa) ^0.5 ,
The method according to the

above aspect

1 or 2.
[4] The induced organic liquid further contains a second solute and / or a desiccant.
The method according to any one of the above aspects 1 to 3.
[5] The dehydration step is executed in a dehydration apparatus including a raw material liquid system for circulating the raw material liquid and an induction liquid system for circulating the induction organic liquid.
The raw material liquid system and the induction liquid system are configured to suppress the movement of the first organic solvent and the second organic solvent to the outside of the system due to vaporization.
The method according to any one of the above aspects 1 to 4.
[6] The second organic solvent is tetrahydrofuran, 2-methyl tetrahydrofuran, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, toluene, cyclopentyl methyl ether, t-butyl methyl ether, acetonitrile, etc. Dimethylacetamide, N-methylpyrrolidone, hexafluoroisopropyl alcohol, acetic acid, acetone, anisole, benzene, chlorobenzene, carbon tetrachloride, chloroform, cumene, cyclohexane, 1,2-dichloroethane, 1,2-dichloroethane, dichloromethane, 1, 2-Dimethoxyethane, N, N-dimethylformamide, dimethylsulfoxide, 1,4-dioxane, ethyl ether, ethyl formate, formamide, formate, formic acid, heptane, hexane, methylbutylketone, methylcyclohexane, methylethylketone, methylisobutylketone, pentane, At least one selected from the group consisting of nitromethane, pyridine, sulfolane, tetralin, 1,1,1-trichloroethane, 1,1,2-trichloroethane, and xylene.
The method according to any one of the above aspects 1 to 5.
[7] In the dehydration step, an organic liquid containing the first organic solvent and having a water content of 0.5% by mass or less is replenished with the raw material liquid whose volume has been reduced by dehydration and concentration.
The method according to any one of the above aspects 1 to 6.
[8] The first solute in the dehydration raw material liquid is subjected to a water-free reaction in which the first solute is chemically reacted with other reagents under anhydrous conditions.
The method according to any one of the above aspects 1 to 7.
[9] The method further comprises a crystallization step of purifying the first solute by crystallization.
The method according to any one of the above aspects 1 to 8.
[10] The method further comprises a liquid separation step of extracting an organic layer from the liquid containing the first solute before the dehydration step.
The organic layer is used as the raw material liquid.
The method according to any one of the above aspects 1 to 9.
[11] The method further comprises a regeneration step.
The regeneration step is a step of removing water transferred from the raw material liquid to the derived organic liquid from the derived organic liquid.
The method according to any one of the above aspects 1 to 10.
[12] In the regeneration step, a desiccant or a dehydrating reagent is added to the induced organic liquid.
The method according to the above aspect 11.
[13] In the regeneration step, the induced organic liquid is dehydrated by azeotropic distillation or membrane treatment.
The method according to the

above aspect

11 or 12.
[14] The method further comprises a crude dehydration step prior to the dehydration step.
In the crude dehydration step, the crude raw material solution and the induced aqueous solution containing the third solute are brought into contact with each other via a forward osmosis membrane to dehydrate the raw material solution to a moisture content of 1% by mass or more and less than 30% by mass. The process of getting
The method according to any one of the above aspects 1 to 13.
[15] The crude dehydration step is executed in a dehydration apparatus including a raw material liquid system for circulating the crude raw material liquid and an induction liquid system for circulating the inductive aqueous solution.
The raw material liquid system is configured to suppress the movement of the first organic solvent to the outside of the system due to vaporization.
The method according to aspect 14 above.
[16] In the crude dehydration step, an organic liquid containing the first organic solvent and having a water content of 0.5% by mass or less is replenished with the crude raw material liquid whose volume has been reduced by dehydration and concentration.
The method according to the above aspect 14 or 15.
[17] The method according to any one of the above aspects 1 to 16, wherein the method is used in the production of a pharmaceutical product.

According to the method according to one aspect of the present invention, a raw material liquid which is an organic solution containing a small amount of water and a solute can be dehydrated under non-heating conditions without decomposing or deteriorating the solute. The method according to one aspect of the present invention is suitably applicable to, for example, dehydrating an organic solution containing a solute in the production of a medicine.

It is a conceptual diagram which shows an example of the dehydration apparatus used in the method which concerns on this invention. It is sectional drawing which shows an example of the forward osmosis membrane module used in the method which concerns on this invention. It is a flowchart which shows the 1st Embodiment of the method which concerns on this invention. It is a flowchart which shows the 2nd Embodiment of the method which concerns on this invention. It is the schematic which shows an example of the apparatus for manufacturing a forward osmosis membrane module.

Hereinafter, an exemplary embodiment for carrying out the present invention (hereinafter, also referred to as the present embodiment) will be described in detail with reference to drawings which are non-limiting examples. The various features shown in the following embodiments can be combined with each other.

≪Outline of dehydration method of organic raw material liquid≫
FIG. 1 is a conceptual diagram showing an example of a dehydrator, FIG. 2 is a sectional view showing an example of a forward osmosis membrane module, and FIGS. 3 and 4 are for explaining the procedure of the method of the present embodiment. It is a flowchart. With reference to FIGS. 1 to 4, the method of the present embodiment is a method for dehydrating the raw material liquid 4 containing the first organic solvent, water and the first solute. In the method of the present embodiment, the raw material liquid 4 and the induced organic liquid 5 containing the second organic solvent are brought into contact with each other via the forward osmosis membrane 23, and the dehydrated raw material liquid is dehydrated to a moisture content of less than 1% by mass. The dehydration step S103 is included. The raw material liquid 4 may be, for example, an organic layer extracted from the liquid containing the first solute in the liquid separation step S101 executed before the dehydration step S103.

The method of the present embodiment may further include a regeneration step S104, which is a step of removing the water transferred from the raw material liquid 4 to the induction organic liquid 5 from the induction organic liquid 5. The induced organic liquid 5 from which water has been removed in the regeneration step S104 is reused in the dehydration step S103 and used for dehydration of the raw material liquid 4.

The dehydration step S103 may be carried out before the water-free reaction step S106 in which the first solute and other reagents are chemically reacted under anhydrous conditions. Further, the method of the present embodiment may further include a crystallization step S105 for purifying the first solute by crystallization. The crystallization step S105 may be carried out before the dehydration step S103, or may be carried out after the dehydration step S103 instead of the water-reactive reaction step S106. Further, the dehydration step S103 may be performed on the reaction solution of the equilibrium reaction. The equilibrium reaction may be a batch type (batch method) or a flow type (continuous method).

The method of the present embodiment may further include a crude dehydration step S102 before the dehydration step S103. Specifically, in the crude dehydration step S102, the crude raw material liquid and the inductive aqueous solution containing the third solute are brought into contact with each other via the forward osmosis membrane 23, so that the water content is 1% by mass or more and less than 30% by mass. This is a step of obtaining the dehydrated raw material liquid 4 of the present embodiment. The crude raw material liquid is, for example, an organic layer extracted in the liquid separation step S101 executed before the crude dehydration step S102.

<< Configuration of dehydrator 1 >>
An example of the configuration of the dehydration apparatus 1 for executing the dehydration step S103 will be described with reference to FIGS. 1 to 4. The dehydrating device 1 is composed of a raw material liquid system 12 and an induction liquid system 13 that come into contact with each other via the forward osmosis membrane module 20. Hereinafter, each component will be described.

<Forward osmosis membrane module 20>
With reference to FIGS. 1 and 2, the forward osmosis membrane module 20 fills a tubular housing 30 with a hollow fiber membrane bundle composed of a plurality of hollow fiber-shaped forward osmosis membranes 23, and an adhesive is applied to both ends of the hollow fiber membrane bundle. It has a structure fixed to the housing 30 by the fixing

portions

24 and 25. The housing 30 is provided with shell-

side conduits

21 and 22 on its side surfaces and

headers

26 and 27 at both ends. Here, the adhesive fixing

portions

24 and 25 are solidified so as not to block the hollow portions of the hollow fibers, respectively.

The

headers

26 and 27 have core-side conduits 28 and 29 that communicate with the hollow portion inside the hollow thread-shaped forward osmosis membrane 23 and do not communicate with the outside of the forward osmosis membrane 23, respectively. The core-side conduits 28 and 29 allow the liquid to be introduced into the forward osmosis membrane 23 and the introduced liquid to be taken out from the inside of the forward osmosis membrane 23. The shell-

side conduits

21 and 22 communicate with the outside of the forward osmosis membrane 23 and not with the inside of the forward osmosis membrane 23, respectively. The shell-

side conduits

21 and 22 allow the liquid to be introduced to the outside of the forward osmosis membrane 23 and the introduced liquid to be taken out from the outside of the forward osmosis membrane 23.

<Raw material liquid system 12>
As shown in FIG. 1, the raw material liquid system 12 includes a raw material liquid tank 2, raw material

liquid feeding pipes

6 and 7, and a raw material liquid feeding pump 8. The raw material liquid tank 2 is filled with the raw material liquid 4, and the raw material liquid 4 circulates in the raw material liquid system 12. Specifically, the raw material liquid 4 passes through the raw material liquid feeding pipe 6 by the raw material liquid feeding pump 8 and enters the forward osmosis membrane module 20 from the core side conduit 28. Then, the raw material liquid 4 passes through the inside of the forward osmosis membrane 23, is discharged from the core side conduit 29, passes through the raw material liquid feeding pipe 7, and returns to the raw material liquid tank 2.

<Induction liquid system 13>
The inductive liquid system 13 includes an inductive liquid tank 3, inductive

liquid feed pipes

9 and 10, and an inductive liquid feed pump 11. The induction liquid tank 3 is filled with the induction organic liquid 5, and the induction organic liquid 5 circulates in the induction liquid system 13. Specifically, the inductive liquid 5 passes through the inductive liquid feed pipe 9 by the inductive liquid feed pump 11, and enters the forward osmosis membrane module 20 from the shell-side conduit 21. Then, the induction organic liquid 5 passes through the outside of the forward osmosis membrane 23, is discharged from the shell-side conduit 22, and returns to the induction liquid tank 3 through the induction liquid delivery pipe 10.

Here, the raw material liquid 4 and the inductive organic liquid 5 are in contact with each other through the wall of the hollow thread-like forward osmosis membrane 23, but they are not directly mixed with each other. Then, when the raw material liquid 4 and the inductive organic liquid 5 come into contact with each other through the wall of the forward osmosis membrane 23, the water in the raw material liquid 4 moves to the inductive organic liquid 5 through the forward osmosis membrane 23, and the raw material The liquid 4 is dehydrated. The flow directions of the raw material liquid 4 and the induced organic liquid 5 in the forward osmosis membrane module 20 may be parallel flow in the same direction through the wall of the forward osmosis membrane 23, and are opposite to each other through the wall of the forward osmosis membrane 23. It may be a countercurrent that is the direction of.

The raw material liquid system 12 and the inductive liquid system 13 are preferably configured so as to suppress the movement of the first and second organic solvents to the outside of the system due to vaporization. Specifically, it is configured so that gas does not leak to the outside from each component of the raw material liquid system 12 and the induction liquid system 13, preferably the raw material liquid tank 2 and the induction liquid tank 3. For example, the raw material liquid tank 2 and the induction liquid tank 3 may be made into tanks with lids, or a condenser for condensing the vaporized organic solvent and returning it to the tank may be installed. A safety valve and / or a back pressure valve may be incorporated in the raw material liquid system 12 and the induction liquid system 13 so that the internal pressures thereof can be adjusted. By preventing the volatilization of the first and second organic solvents, it is possible to prevent an increase in the water content of the raw material liquid 4 and the induced organic liquid 5, and it is possible to efficiently dehydrate.

<Forward osmosis membrane 23>
As the forward osmosis membrane 23, a membrane having the property of a semipermeable membrane through which water can pass can be used without limitation. The forward osmosis membrane 23 is preferably a composite type membrane having a separation active layer on the support layer (support membrane) from the viewpoint of ensuring high membrane strength. The support membrane may be a flat membrane or a hollow fiber membrane. When the support membrane is a flat membrane, it may have a separation active layer on one side or both sides of the support membrane. When the support film is a hollow fiber membrane, a separation active layer may be provided on the outer surface or inner surface of the hollow fiber membrane, or both surfaces.

It is convenient to modularize the forward osmosis membrane 23 as described above. The normal osmotic membrane module 20 can be, for example, a pleated type module, a spiral type module, etc. when the normal permeable membrane is a flat membrane, and for example, when the normal permeable membrane is a hollow fiber membrane, for example. It can be a hollow fiber membrane module or the like in which a bundle of the hollow fiber membranes is filled in a cylinder. Here, the forward osmosis membrane module 20 is preferably a module in which a bundle of forward osmosis membranes 23, which is a hollow fiber membrane, is filled in a cylinder.

The support film is preferably a microporous hollow fiber support film. The microporous hollow fiber support membrane has fine pores having a pore diameter of preferably 0.001 μm or more and 2 μm or less, more preferably 0.001 μm or more and 0.2 μm or less on the inner surface thereof. As the material of the microporous hollow fiber support membrane, a material used for an ultrafiltration membrane, a microfiltration membrane, or the like may be utilized. Specifically, the material of the hollow thread support film is, for example, polysulfone, polyethersulfone, polyvinylidene fluoride, polyacrylonitrile, polyethylene, polypropylene, cellulosic polymer, polybenzoimidazole, polyketone, polyamide, polyimide, polyether ether ketone. , And these crosslinked bodies and the like, and preferably contains at least one selected from these, and / or one selected from these is the main component (that is, the component having the highest content). The material of the hollow fiber support membrane contains at least one selected from polysulfone, polyethersulfone, polyketone, polyamide, polyimide, and a crosslinked product thereof, and / or one selected from these is the main component. Is more preferable, and more preferably polyketone.

The separation active layer contains and / or is selected from at least one polymer selected from, for example, polysulfone, polyethersulfone, polyvinylidene fluoride, polyacrylonitrile, polyethylene, polypropylene, polyamide, polyimide, cellulose acetate and the like. A thin film layer containing only one type as a main component is preferably used. These polymers may or may not be crosslinked. When the separation active layer is a crosslinked polymer, the degree of crosslinking may be arbitrary. Considering the dehydration efficiency of the raw material liquid 4, the ease of formation on the support layer, and the like, the separation active layer is preferably a layer of polyamide, and one or more selected from non-crosslinked polyamide and crosslinked polyamide is used. good. The polyamide constituting the separation active layer can be formed, for example, by interfacial polymerization of a polyfunctional aromatic acid halide and a polyfunctional aromatic amine.

A polyfunctional aromatic acid halide is an aromatic acid halide compound having two or more acid halide groups in one molecule. Specifically, for example, trimesic acid halide, trimellitic acid halide, phthalic acid halide, isophthalic acid halide, terephthalic acid halide, pyromellitic acid halide, benzophenonetetracarboxylic acid halide, biphenyldicarboxylic acid halide, naphthalenedicarboxylic acid halide, pyridine. Examples thereof include dicarboxylic acid halide, benzenedisulfonic acid halide and the like, and one of these or a mixture of two or more thereof can be used. In the present invention, trimesic acid chloride alone, a mixture of trimesic acid chloride and isophthalic acid chloride, or a mixture of trimesic acid chloride and terephthalic acid chloride is particularly preferably used.

The polyfunctional aromatic amine is an aromatic amino compound having two or more amino groups in one molecule. Specifically, for example, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3 , 3'-diaminodiphenylamine, 3,5-diaminobenzoic acid, 4,4'-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 1,3,5-tri Aminobenzene, 1,5-diaminonaphthalene and the like can be mentioned, and one or a mixture of two or more of these can be used. In this embodiment, in particular, one or more selected from m-phenylenediamine and p-phenylenediamine are preferably used.

<Raw material liquid 4>
The raw material liquid 4 is an organic solution containing a first organic solvent, water and a first solute. Here, the initial water content of the raw material liquid 4 in the dehydration step S103 is 1% by mass or more and less than 30% by mass, preferably 1% by mass or more and less than 20% by mass, and more preferably 1% by mass or more and 15% by mass. It is less than% by mass. Here, the "initial moisture content" is the raw material liquid 4 or the induced organic liquid at the time when the raw material liquid 4 is prepared in the raw material liquid tank 2 or the induction organic liquid 5 is prepared in the induction liquid tank 3. It refers to the water content of 5, and is the same in the following. The method for measuring the water content will be described later.

The first organic solvent may be an ether (for example, cyclic ether), an ester, a hydrocarbon, a nitrogen-containing compound, a sulfur-containing compound, a halogen compound, a ketone, or the like, and specifically, tetrahydrofuran, 2-methyl tetrahydrofuran, acetic acid or the like. Methyl, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, toluene, cyclopentyl methyl ether, t-butyl methyl ether, acetonitrile, dimethylacetamide, N-methylpyrrolidone, hexafluoroisopropyl alcohol, acetic acid, acetone, anisole, Benzene, chlorobenzene, carbon tetrachloride, chloroform, cumene, cyclohexane, 1,2-dichloroethane, 1,2-dichloroethane, dichloromethane, 1,2-dimethoxyethane, N, N-dimethylformamide, dimethylsulfoxide, 1,4- Dioxane, ethyl ether, ethyl formate, formamide, formate, heptane, hexane, methylbutylketone, methylcyclohexane, methylethylketone, methylisobutylketone, pentane, nitromethane, pyridine, sulfolane, tetraline, 1,1,1-trichloroethane, 1,1 , 2-Trichloroether, at least one selected from the group consisting of xylene. The first organic solvent is preferably at least one selected from the group consisting of tetrahydrofuran, 2-methyl tetrahydrofuran, ethyl acetate, isopropyl acetate, toluene, cyclopentyl methyl ether, and t-butyl methyl ether, more preferably. Is at least one selected from the group consisting of tetrahydrofuran, ethyl acetate, isopropyl acetate, toluene, and t-butyl methyl ether, and more preferably selected from the group consisting of tetrahydrofuran, ethyl acetate, and isopropyl acetate. At least one species.

The first solute may be a substance that does not pass through the forward osmosis membrane 23, and is not limited to a specific type. The method of this embodiment is used in the manufacture of a pharmaceutical in one embodiment. The first solute is, for example, a raw material used in the pharmaceutical industry or the like (for example, amino acids such as phenylalanine, sugars such as sucrose, natural products such as alkaloids isolated from nature such as quinine, compounds called building blocks, etc.). , Intermediate compounds (eg, compounds chemically synthesized or modified from raw materials such as octaacetylsucrose), or final compounds (eg, drug substance) (eg, small molecule drugs, medium molecule drugs such as peptides or nucleic acids, proteins Such as high-molecular-weight drugs, vaccines, antibiotics, etc.). The solute may be a solid, a liquid, or a mixture of a plurality of substances. The first organic solvent and the first solute are selected so as to be different substances.

The molecular weight of the first solute is preferably 100 or more and 30,000 from the viewpoint of preventing the first solute from penetrating the forward osmosis membrane 23 and preventing the first solute from adhering to the forward osmosis membrane 23. Hereinafter, it is more preferably 150 or more and 10000 or less, and further preferably 200 or more and 1000 or less. When the valuable resource is a polymer, the molecular weight is a number average molecular weight in terms of polyethylene oxide measured by gel permeation chromatography, and when it is not a polymer, it refers to a value based on the atomic weight. The concentration of the solute is not limited to a specific value, and may be appropriately selected within a range soluble in the first organic solvent. Specifically, for example, 0.1% by mass or more and 60% by mass or less, preferably 1% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 40% by mass or less, based on the total mass of the raw material liquid 4. It may be: By setting the concentration of the first solute to a predetermined value or higher, the amount of the solute that can be processed at one time in the dehydrator 1 can be increased and the treatment efficiency can be improved. The raw material liquid 4 can be circulated in the dehydrator 1 without precipitating the solute.

<Induced organic liquid 5>
The derived organic liquid 5 contains a second organic solvent. Here, the second organic solvent is an organic liquid that does not permeate the forward osmosis membrane 23. Since the inducing organic liquid 5 is not an aqueous solution but an organic liquid containing a second organic solvent that does not permeate the forward osmosis film 23, it is possible to prevent the diffusion of water from the inductive organic liquid 5 to the raw material liquid 4, and a small amount of water can be prevented. The raw material liquid 4 containing water can be effectively dehydrated.

The difference ΔHSP between the inducible organic solution 5 and the separable active layer of the forward osmosis membrane 23 is preferably ΔHSP <16 (MPa) ^0.5 . When the inducing organic liquid and the separation active layer satisfy this condition, it is considered that dehydration can be suitably performed by appropriately swelling the separation active layer and increasing the permeation path of water. The ΔHSP is more preferably 15 (MPa) ^0.5 or less, or 14 (MPa) ^0.5 or less, or 13 (MPa) ^0.5 or less. It is preferable that ΔHSP is small, but from the viewpoint of convenience when selecting the combination of the induced organic liquid and the separation active layer, in one embodiment, 5 (MPa) ^0.5 or more, or 6 (MPa) ^0.5 or more, or 7 ( MPa) ^0.5 or more.

The solubility parameter of the present disclosure is the Hansen solubility parameter (HSP). Based on the dispersion term δd, polar term δp, and hydrogen bond term δH of HSP, the solubility parameter difference ΔHSP between two substances can be calculated by the following formula.

Regarding the HSP value of the separation active layer, the chemical structure of the polymer constituting the separation active layer is converted into a monomer by the procedure shown below, and the HSP of the monomer is converted into a Hansen SP & QSPR model which is an add-on of the commercially available software Winmostar 9.4.11. This value can be regarded as the HSP of the isolation active layer. For example, in the case of a non-crosslinked polymer having a linear structure and no branched chain, the repeating unit of the polymer is taken out, the bonding portion between the repeating units is replaced with a methyl group, and then the HSP of the monomer is calculated. do. On the other hand, in the case of a crosslinked polymer having a branched chain, the repeating unit is taken out, and all the functional groups that may remain unreacted without being crosslinked except at the end of the polymer are replaced with hydrogen groups to form a linear structure. After conversion to the polymer and the repeating unit of the above, the HSP of the monomer is calculated after replacing the bonding portion between the repeating units after the conversion with a methyl group. The specific procedure will be described later.

Regarding the HSP value of the induced organic liquid, the HSP value of the entire induced organic liquid is obtained from the HSP of each of the n kinds of liquid components (

components

1, 2, ... N) contained in the induced organic liquid and the volume fraction in the induced organic liquid. Can be determined. Specifically, the calculation is performed according to the following formula. The solid component contained in the induced organic liquid is not considered in the calculation of the HSP value.

(During the ceremony
V1, V2, ... Vn is the volume fraction of each of the

components

1, 2, ... n.
δd1, δd2, ... δdn is the dispersion term of each HSP of the

components

1, 2, ... N.
δp1, δp2, ... δpn is the polar term of each HSP of the

components

1, 2, ... N.
δH1, δH2, ... δHn are hydrogen bond terms of each HSP of the

components

1, 2, ... n. )

The HSP value of each liquid component of the induced organic liquid can be calculated using the Hansen SP & QSPR model, which is an add-on of the commercially available software Winmostar 9.4.11.

The solubility parameter (HSP) value of the separation active layer is preferably 15 (MPa) ^0.5 or more, 16 (MPa) ^0.5 or more, or 17 (MPa) ^0.5 or more, and preferably 40 (MPa) ^0.5 or less. Or 39 (MPa) ^0.5 or less, or 38 (MPa) ^0.5 or less.

The solubility parameter (HSP) value of the derived organic liquid is preferably 13 (MPa) ^0.5 or more, or 14 (MPa) ^0.5 or more, or 15 (MPa) ^0.5 or more, and preferably 39 (MPa) ^0.5 or less. Or 38 (MPa) ^0.5 or less, or 37 (MPa) ^0.5 or less.

In the solubility parameter of the separation active layer, δd is preferably 15 (MPa) ^0.5 or more, or 16 (MPa) ^0.5 or more, or 17 (MPa) ^0.5 or more, preferably 26 (MPa) ^0.5 or less, or 25. (MPa) ^0.5 or less, or 24 (MPa) ^0.5 or less, and δp is preferably 2 (MPa) ^0.5 or more, or 3 (MPa) ^0.5 or more, or 4 (MPa) ^0.5 or more, preferably 26 ( MPa) ^0.5 or less, or 25 (MPa) ^0.5 or less, or 24 (MPa) ^0.5 or less, and δH is preferably 1 (MPa) ^0.5 or more, or 2 (MPa) ^0.5 or more, or 3 (MPa) ^0.5 . The above is preferably 20 (MPa) ^0.5 or less, 19 (MPa) ^0.5 or less, or 18 (MPa) ^0.5 or less.

In the solubility parameter of the induced organic solution, δd is preferably 13 (MPa) ^0.5 or more, or 14 (MPa) ^0.5 or more, or 15 (MPa) ^0.5 or more, preferably 20 (MPa) ^0.5 or less, or 19. (MPa) ^0.5 or less, or 18 (MPa) ^0.5 or less, and δp is preferably 2 (MPa) ^0.5 or more, or 3 (MPa) ^0.5 or more, or 4 (MPa) ^0.5 or more, preferably 18 ( MPa) ^0.5 or less, or 17 (MPa) ^0.5 or less, or 16 (MPa) ^0.5 or less, and δH is preferably 2 (MPa) ^0.5 or more, or 3 (MPa) ^0.5 or more, or 4 (MPa) ^0.5 . The above is preferably 28 (MPa) ^0.5 or less, 27 (MPa) ^0.5 or less, or 26 (MPa) ^0.5 or less.

The saturated water content of the induced organic liquid is preferably 0.5% by mass or more, 1.0% by mass or more, or 2.0% by mass or more. It is considered that when the induced organic liquid satisfies this condition, water can be suitably transferred from the raw material liquid to the induced organic liquid. The saturated water content is preferably 100% (that is, optionally mixed with water), but from the viewpoint of dehydration efficiency, for example, even if it is 99% by mass or less, 98% by mass or less, or 97% by mass or less. good.

The saturated water content of the induced organic liquid can be determined by the following procedure. Water and the induced organic liquid are mixed in equal amounts using a separatory funnel in terms of weight. If it is not divided into two layers, an aqueous layer and an organic layer, the induced organic liquid is considered to be miscible with water at an arbitrary ratio. When separated into two layers, the liquid is then separated, and the water content of the obtained organic layer is regarded as the saturated water content. The method for measuring the water content will be described later.

If the saturated water content of the induced organic liquid is unknown and the induced organic liquid contains a solvent that is arbitrarily mixed with water, water is added little by little to the induced organic liquid, and the amount of water added just before the two phases are formed. From (g) and the amount of the derived organic liquid used (g), the water content obtained by the following formula is defined as the saturated water content.

The dehydration efficiency can be calculated based on the following formula based on the water content of the raw material liquid (FS) and the amount of the raw material liquid (FS). For the t minutes below, it is preferable to select about one-eighth to one-fourth of the total operating time. From the dehydration efficiency at the initial stage of operation, the degree of dehydration after the end of operation can be estimated.

For example, when the first solute and / or the second solute is precipitated during operation, the dehydration efficiency is modified as follows. When the solute precipitation is confirmed, the operation is stopped and the total weight (A) of the raw material liquid is measured. Then, the water content of the supernatant is measured. This water content is taken as the water content of the raw material liquid (FS) after t minutes. Further, the precipitated solute is filtered off, and the precipitated weight (B) is measured. The weight of (A)-(B) is defined as the amount of raw material liquid (FS) after t minutes.

The second organic solvent may be ether (for example, cyclic ether), ester, hydrocarbon, nitrogen-containing compound, sulfur-containing compound, halogen compound, ketone, alcohols and the like, and specifically, tetrahydrofuran and 2-methyl. Tetrahydrofuran, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, toluene, cyclopentyl methyl ether, t-butyl methyl ether, acetonitrile, dimethylacetamide, N-methylpyrrolidone, hexafluoroisopropyl alcohol, acetate, acetone , Anisole, benzene, chlorobenzene, carbon tetrachloride, chloroform, cumene, cyclohexane, 1,2-dichloroethane, 1,2-dichloroethane, dichloromethane, 1,2-dimethoxyethane, N, N-dimethylformamide, dimethylsulfoxide, 1 , 4-dioxane, ethyl ether, ethyl formate, formamide, formate, heptane, hexane, methylbutylketone, methylcyclohexane, methylethylketone, methylisobutylketone, pentane, nitromethane, pyridine, sulfolane, tetraline, 1,1,1-trichloroethane, At least one selected from the group consisting of 1,1,2-trichloroethane, xylene, methanol, ethanol, and isopropyl alcohol. The second organic solvent is preferably at least one selected from the group consisting of tetrahydrofuran, 2-methyl tetrahydrofuran, ethyl acetate, isopropyl acetate, toluene, cyclopentyl methyl ether, and t-butyl methyl ether, more preferably. Is at least one selected from the group consisting of tetrahydrofuran, ethyl acetate, isopropyl acetate, toluene, and t-butyl methyl ether, and more preferably selected from the group consisting of tetrahydrofuran, ethyl acetate, and isopropyl acetate. At least one species.
The first organic solvent and the second organic solvent may be the same or different from each other.

The initial water content of the induced organic liquid 5 in the dehydration step S103 is smaller than the initial water content of the raw material liquid 4. Here, when the derived organic liquid 5 contains a second solute and / or a desiccant, the initial water content of the induced organic liquid 5 is measured in a state where these are added. In the induced organic liquid 5 containing a desiccant, a portion other than the desiccant (specifically, a supernatant portion) is sampled to measure the water content. However, when the induction organic liquid 5 contains a dehydration reagent as the second solute, the state before the addition of the dehydration reagent, that is, the liquid lacking the dehydration reagent among the constituents of the induction organic liquid (in one embodiment, the second organic solvent). ) Is regarded as the water content of the induced organic liquid 5. Since the forward osmosis membrane is a semipermeable membrane that allows water to permeate, it is conceivable that water moves from the raw material liquid 4 side having many water molecules to the induced organic liquid 5 side having few water molecules due to the diffusion phenomenon. Thereby, a small amount of water contained in the raw material liquid 4 which is an organic solution can be removed. In one embodiment, the difference between the initial water content (mass%) of the induced organic liquid 5 and the initial water content (mass%) of the raw material liquid 4 in the dehydration step S103 is 0.5% by mass or more, or 0. It may be 7% by mass or more, or 1% by mass or more, and in one embodiment, it may be 20% by mass or less, 15% by mass or less, or 10% by mass or less.

The induction organic liquid 5 may further contain a second solute and / or a desiccant. The second solute is a substance that is soluble in or completely mixed with the second organic solvent and does not permeate the forward osmosis membrane. The second solute may be at least partially dissolved in or completely mixed with the second organic solvent at a concentration in the derived organic liquid 5. On the other hand, the desiccant removes water by physically adsorbing water in the solution, or takes in water as water of crystallization and removes water. The desiccant may be a substance soluble or insoluble in the induced organic liquid 5. The desiccant is, in one embodiment, a substance that remains solid in the induced organic liquid 5 at 20 ° C. containing the second organic solvent, and more typically a substance that is insoluble in the second organic solvent. .. With the desiccant, the water that has permeated the forward osmosis membrane 23 from the raw material liquid 4 can be removed from the induced organic liquid 5, and the raw material liquid 4 can be dehydrated more efficiently.

Specific examples of the second solute include: monoalcohols having a branch of 3 carbon atoms such as 2-propanol, 2-butanol, 2-methyl-2-propanol, and monoalcohols having 4 or more carbon atoms; toluene and the like. Non-polar solvent; Polymers such as polyethylene glycol and polypropylene glycol; Dehydration reagents such as orthoester, sodium, calcium hydride, diphosphorus pentoxide; Organic acids such as paratoluenesulfonic acid and pyridinium paratoluenesulfonate; One or more selected. Here, the dehydrating reagent removes water by chemically reacting with water in the solution, and is distinguished from the above-mentioned desiccant which does not involve a chemical reaction at the time of dehydration. The orthoester may be, for example, trimethyl orthoformate, triethyl orthoformate or the like. The second organic solvent and the second solute are selected so as to be different substances.

The second solute is preferably selected from: orthoester dehydration reagents such as trimethyl orthogitate, triethyl orthogeate; and compounds having a toluene structure such as toluene, paratoluenesulfonic acid, pyridinium paratoluenesulfonate; One or more, more preferably one or more selected from trimethyl orthogeate, triethyl orthogeate, paratoluenesulfonic acid, and pyridinium paratoluenesulfonate, still more preferably triethyl orthogeate and It is paratoluene sulfonic acid or pyridinium paratoluene sulfonic acid. It is considered that the osmotic pressure of the induced organic liquid 5 can be increased and the dehydration effect of the raw material liquid 4 can be enhanced by containing the second solute in the induced organic liquid 5. A compound having a hydrophobic structure such as a toluene structure may have a good effect of increasing the osmotic pressure of the induced organic liquid 5 due to the contribution of the hydrophobic structure.

The concentration of the second solute contained in the derived organic liquid 5 may be 0.01% by mass or more, 0.1% by mass or more, or 1% by mass or more in one embodiment, and 60% by mass in one aspect. % Or less, or 50% by mass or less, or 40% by mass or less, or 30% by mass or less, or 20% by mass or less, or 10% by mass or less. The concentration of the polymer such as polyethylene glycol and polypropylene glycol contained in the derived organic liquid 5 is preferably 0.1% by mass or more and 60% by mass or less, more preferably 60% by mass or less, based on the total mass of the induced organic liquid 5. It is 0.5% by mass or more and 50% by mass or less. By setting the concentration of the polymer to a predetermined value or higher, the osmotic pressure of the induced organic liquid 5 can be further increased, and by setting the concentration to a predetermined value or lower, the induced organic liquid 5 is suitable for circulating in the dehydrator 1. The viscosity can be adjusted. The concentration of the ortho ester-based dehydration reagent contained in the derived organic liquid 5 is preferably 1% by mass or more and 60% by mass or less, and more preferably 5% by mass or more and 40% by mass, based on the total mass of the induced organic liquid 5. It is less than mass%. By setting the concentration of the ortho ester-based dehydrating reagent to a predetermined value or higher, the water transferred from the raw material liquid 4 to the induced organic liquid 5 can be satisfactorily removed, and by setting the concentration to a predetermined value or lower, the reaction heat of the dehydrating reagent can be satisfactorily removed. It is possible to prevent deterioration of the forward osmosis film 23 due to the above. The amount of the organic acid contained in the derived organic liquid 5 may be a catalytic amount, preferably 0.01% by mass or more and 10% by mass or less with respect to the total mass of the induced organic liquid 5, and more preferably. It is 0.1% by mass or more and 5% by mass or less.

Examples of the desiccant include porous materials such as silica gel and molecular sieve, and hydrate-forming compounds such as sodium sulfate and magnesium sulfate, which are generally used for dehydration of organic solvents. The desiccant is preferably one or more selected from the group consisting of molecular sieves and magnesium sulfate, and more preferably molecular sieves. The amount of the desiccant contained in the derived organic liquid 5 is preferably 1% by mass or more and 60% by mass or less, and more preferably 5% by mass or more and 50% by mass or less, based on the total mass of the induced organic liquid 5. Is. By setting the amount of the desiccant to a predetermined value or more, the water transferred from the raw material liquid 4 to the induction organic liquid 5 can be satisfactorily removed, and by setting the amount to a predetermined value or less, the water inside the induction liquid tank 3 can be satisfactorily removed. The pressure loss can be reduced.

<< Method according to the first embodiment >>
The method according to the first embodiment will be described with reference to FIG. This method assumes, for example, in the production of pharmaceuticals, a procedure in which an organic layer containing water is extracted by liquid separation, dehydrated to a desired amount of water, and then crystallized or a water-free reaction is carried out.

In the liquid separation step S101 in FIG. 3, an organic solution containing the first solute, which is a product of a certain chemical reaction, is extracted by a liquid separation operation. Since the organic solution extracted by the liquid separation operation contains water, it is dehydrated in the crude dehydration step S102 and the dehydration step S103. When the water content of the organic solution is 1% by mass or more and less than 30% by mass, preferably 1% by mass or more and less than 20% by mass, more preferably 1% by mass or more and less than 15% by mass, the crude dehydration step S102 is omitted and dehydration is performed. Step S103 may be executed.

In the crude dehydration step S102 in FIG. 3, the crude raw material solution, which is the organic solution extracted in the liquid separation step S101, and the inductive aqueous solution containing the third solute are brought into contact with each other via the forward osmosis membrane 23 to obtain water content. A raw material solution 4 dehydrated to a ratio of 1% by mass or more and less than 30% by mass is obtained. The time of the dehydration step S103 can be shortened by dehydrating to a certain extent using an aqueous inductive aqueous solution that is harder to vaporize than an organic solvent and can be easily handled.

Here, the third solute may be, for example, one or more selected from the group consisting of halides, nitrates, sulfates, acetates, ureas, alcohols, glycols, polymers, and sugars. Specifically, for example, sodium chloride, potassium chloride, magnesium chloride, ammonium chloride, potassium nitrate, ammonium nitrate, sodium sulfate, magnesium sulfate, ammonium sulfate, sodium acetate, potassium acetate, methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol. , Propylene glycol, polyethylene glycol, and one or more selected from the group consisting of polypropylene glycol.

The crude dehydration step S102 is executed in the dehydration apparatus 1 including the raw material liquid system 12 for circulating the crude raw material liquid and the induction liquid system 13 for circulating the inductive aqueous solution. Here, preferably, the raw material liquid system 12 is configured to suppress the movement of the first organic solvent to the outside of the system due to vaporization. By preventing the volatilization of the first organic solvent, it is possible to prevent an increase in the water content of the raw material liquid 4.

Preferably, in the crude dehydration step S102, an organic liquid containing the first organic solvent and having a water content of 0.5% by mass or less is replenished with the crude raw material liquid whose volume has been reduced by dehydration and concentration. By replenishing the reduced volume of the raw material liquid 4 with the organic liquid, the water content of the raw material liquid 4 can be further reduced. The water content of the organic liquid may be 0.4% by mass or less or 0.3% by mass or less, and from the viewpoint of availability of the organic liquid, 0.001% by mass or more or 0.01% by mass or more. , Or 0.1% by mass or more.

In the dehydration step S103 in FIG. 3, first, a raw material liquid 4 which is an organic solution roughly dehydrated in the crude dehydration step S102 and a second organic solvent are contained, and an induced organic having a water content smaller than that of the raw material liquid 4 is provided. Prepare liquid 5. Then, the raw material liquid 4 and the induced organic liquid 5 are brought into contact with each other via the forward osmosis membrane 23 to obtain a dehydrated raw material liquid dehydrated to a water content of less than 1% by mass. The dehydration method of the present embodiment can shorten the time required for dehydration as compared with the conventional dehydration method in which the organic solution extracted by liquid separation is concentrated by azeotrope, and the first solute is decomposed by heating or Deterioration can be prevented. The water content of the dehydration raw material solution is preferably 0.95% by mass or less, or 0.9% by mass or less, or 0.85% by mass or less, or 0.8% by mass or less, or 0.75% by mass or less. Or 0.7% by mass or less. It is preferable that the water content of the dehydration raw material liquid is low, but from the viewpoint of process efficiency, in one embodiment, 0.01% by mass or more, 0.05% by mass or more, or 0.1% by mass or more, or 0.2. It may be mass% or more, 0.3 mass% or more, or 0.4 mass% or more.

The dehydration step S103 is executed in the dehydration apparatus 1 including the raw material liquid system 12 that circulates the raw material liquid 4 and the induction liquid system 13 that circulates the induction organic liquid 5. Here, preferably, the raw material liquid system 12 and the inductive liquid system 13 are configured to suppress the movement of the first and second organic solvents to the outside of the system due to vaporization. As a result, volatilization of the first and second organic solvents can be prevented, and an increase in the water content of the raw material liquid 4 and the induced organic liquid 5 can be prevented.

Preferably, in the dehydration step S103, an organic liquid containing the first organic solvent and having a water content of 0.5% by mass or less is replenished with the raw material liquid 4 whose volume has been reduced by dehydration and concentration. By replenishing the reduced volume of the raw material liquid 4 with the organic liquid, the water content of the raw material liquid 4 can be further reduced. The water content of the organic liquid may be 0.4% by mass or less or 0.3% by mass or less, and from the viewpoint of availability of the organic liquid, 0.001% by mass or more or 0.01% by mass or more. , Or 0.1% by mass or more.

In the regeneration step S104 in FIG. 3, the water transferred from the raw material liquid 4 to the inductive organic liquid 5 is removed from the inductive organic liquid 5 in order to obtain the inductive organic liquid 5 that can be reused in the dehydration step S103. After the regeneration step S104, the dehydration step S103 may be executed again using the induced organic liquid 5 treated in the regeneration step S104. As a result, dehydration can be performed while maintaining a state in which the osmotic pressure of the induced organic liquid 5 is higher than that of the raw material liquid 4, and the final water content of the dehydrated raw material liquid can be made smaller.

In the regeneration step S104, the induced organic liquid 5 is preferably dehydrated by azeotropic distillation or membrane treatment. Here, the azeotropic distillation may be vacuum distillation or the like. Here, the membrane treatment may be a method of removing water from the induced organic liquid 5 by evaporating it using an osmotic vaporized membrane that selectively permeates water. More preferably, in the regeneration step S104, a desiccant or a dehydrating reagent is added to the inducing organic liquid 5. As the desiccant and dehydration reagent, the above-mentioned substances are preferably used.

Next, the crystallization step S105 or the water-reactive reaction step S106 is executed. In the crystallization step S105 in FIG. 3, the first solute is separated by crystallization from the dehydration raw material liquid obtained in the dehydration step S103 and purified. Crystallization may be carried out by methods commonly used by those skilled in the art. Preferably, in order to prevent alteration of the first solute due to heating or pressure manipulation, a method of cooling the dehydration raw material solution or a method of adding a solvent in which the first solute is poorly soluble is added to the dehydration raw material solution.

In the water-free reaction step S106 in FIG. 3, another reagent is added to the dehydration raw material solution obtained in the dehydration step S103, and the chemical reaction is allowed to proceed under anhydrous conditions. The chemical reaction in the water-inhibited reaction step S106 is a water-inhibited reaction in which the progress of the desired reaction is inhibited in the presence of water. Here, the other reagent may be, for example, an organometallic reagent such as a Grignard reagent or butyllithium.

<< Method according to the second embodiment >>
As a method according to the second embodiment with reference to FIG. 4, a procedure in which a solute is crystallized from an aqueous solution, the obtained wet crystal is dissolved in an organic solvent, dehydrated, and then a water-free reaction is carried out in the production of a pharmaceutical product. The assumed method will be explained.

In the crystallization step S105 in FIG. 4, wet crystals, which are the first solute containing water, are separated from the aqueous solution containing the first solute, which is the product of a certain chemical reaction. The obtained wet crystals are dissolved in the first organic solvent to obtain a crude raw material liquid and a raw material liquid 4 to be dehydrated in the crude dehydration step S102 and the dehydration step S103. The rough dehydration step S102 may be omitted. The dehydration method of the present embodiment can shorten the time required for dehydration as compared with the conventional dehydration method in which wet crystals are heated under reduced pressure and dried, and the decomposition or alteration of the first solute by heating can be performed. Can be prevented.

The crude dehydration step S102, the dehydration step S103, the regeneration step S104, and the water-reactive reaction step S106 in FIG. 4 may be the same as those in the first embodiment, and therefore the description is not repeated.

Hereinafter, the present invention will be specifically described based on Examples, but the present invention is not limited to Examples.

≪Experimental method≫
(Preparation of forward osmosis membrane module)
A polyketone having an extreme viscosity of 2.2 dL / g, in which ethylene and carbon monoxide were completely alternately copolymerized, was added to a 65% by mass resorcin aqueous solution so that the polymer concentration was 15% by mass, and dissolved by stirring at 80 ° C. for 2 hours. , Defoaming was performed to obtain a uniform and transparent undiluted spinning solution. A wet hollow fiber spinning machine equipped with a double spinner is filled with the above-mentioned spinning stock solution, and a 25% by mass methanol aqueous solution is charged from the inside of the double spinning spout, and the above spinning stock solution is filled with 40% by mass methanol from the outside. It was extruded into a coagulation tank filled with an aqueous solution, and a hollow fiber membrane was formed by phase separation.

The obtained hollow fiber membrane was cut to a length of 70 cm, bundled, and washed with water. The hollow fiber membrane bundle after washing with water was subjected to solvent substitution with acetone, solvent substitution with hexane, and then drying at 50 ° C. The polyketone hollow fiber membrane thus obtained had an outer diameter of 0.8 mm, an inner diameter of 0.5 mm, a void ratio of 78%, and a maximum pore diameter of the membrane wall of 130 nm. The hollow fiber membrane bundle composed of the 80 polyketone hollow fiber membranes is housed in a cylindrical module housing (cylindrical case) having a diameter of 2 cm and a length of 10 cm, and both ends of the hollow fiber membrane bundle are fixed with an adhesive. To prepare a polyketone hollow fiber support membrane module.

Using the obtained polyketone hollow fiber support membrane module, interfacial polymerization was carried out on the inner surface of each hollow fiber membrane as follows. 20.216 g of m-phenylenediamine and 1.52 g of sodium lauryl sulfate were placed in a 1 L container, and 991 g of pure water was further added and dissolved to prepare a first solution to be used for interfacial polymerization. In another 1 L container, 0.6 g of trimesic acid chloride was placed, and 300 g of n-hexane was added and dissolved to prepare a second solution used for interfacial polymerization.

The method of forming the separation active layer by interfacial polymerization will be described with reference to FIG. In the apparatus shown in FIG. 5, the hollow fiber support membrane module 41 in which the inside (core side) of the hollow fiber support membrane is filled with the first solution has a second solution from the second solution storage tank 44 at the entrance on the core side. The liquid feeding pipe 45 is connected, and the second solution liquid feeding pump 46 for pumping the second solution is connected in the middle. The second solution drainage pipe 48 from the second solution drainage tank 47 is connected to the outlet on the core side, and the core side pressure adjustment that controls the pressure inside the hollow fiber of the hollow fiber support membrane module 41 from the tank. The device 42 is connected. An end cap 49 is fitted in the lower conduit on the shell side of the hollow fiber support membrane module 41, and a shell-side pressure adjusting device 43 for controlling the shell pressure is connected to the upper conduit. FIG. 5 shows the core side (inside of the hollow fiber) of the hollow fiber support membrane module 41 filled with the first solution, allowed to stand for 5 minutes, then drained, and the inside of the hollow fiber is wet with the first solution. It was attached to the device shown in. The core side pressure was set to normal pressure by the core side pressure adjusting device 42, and the shell side pressure was set to a reduced pressure of 10 kPa as an absolute pressure by the shell side pressure adjusting device 43 (core side pressure> shell side pressure). After allowing to stand for 2 minutes in this state, the second solution was fed to the core side at a flow rate of 40 cc / min for 3 minutes by the second solution feed pump 46 while maintaining this pressure, and interfacial polymerization was performed. The polymerization temperature was 25 ° C.

Next, the hollow fiber support membrane module was removed from the apparatus and allowed to stand in a constant temperature bath set at 50 ° C. for 5 minutes to vaporize and remove n-hexane. Further, a forward osmosis membrane module was produced by washing both the shell side and the core side with pure water.

(Calculation of HSP)
The HSP of the isolated active layer was modeled and calculated as follows. Generally, the repeating unit of the separation active layer obtained by interfacial polymerization by this method is the following formula (1):

(In the formula, x and y are each independently an integer of 1 or more.)
It is represented by.

As represented by the above formula (1), the separation active layer has a structure in which a part of the trimesic acid chloride-derived portion is crosslinked and a part is not crosslinked (that is, hydrolyzed). Have.

In the above polymer structure, first, a functional group that may remain unreacted without cross-linking other than at the end of the polymer (that is, a hydrolyzable structural portion, that is, a hydrolyzed structural moiety and a branched chain at a repeating unit. All the structural parts forming the above are replaced with hydrogen groups. As a result, the following equation (2):

The structure represented by is obtained. Next, in the above polymer structure, the portion related to the chemical bond of the repeating unit is replaced with a methyl group. As a result, the following equation (3):

The monomer structure represented by is obtained.
The HSP of the monomer structure obtained by the above modeling was calculated using the Hansen SP & QSPR model, which is an add-on of the commercially available software Winmostar 9.4.11. As a result, δd = 20.5 (MPa) ^0.5 , δp = 11.47 (MPa) ^0.5 , δH = 7.22 (MPa) ^0.5 , and HSP was 24.58 (MPa) ^0.5 .
The HSP of the second organic solvent of the derived organic liquid was also calculated using the Hansen SP & QSPR model, which is an add-on of the commercially available software Winmostar 9.4.11, in the same manner as described above.
The results are summarized in Table 1.

(Measurement of water content)
Take about 0.5 mL of the raw material solution, crude raw material solution, or inductive organic solution with a 1 mL syringe, and inject about 0.1 mL into the Karl Fischer Moisture Measuring Device (type CA-200, manufactured by Mitsubishi Chemical Analytech Co., Ltd.). The water content was measured. In Examples 4 and 6 in which the molecular sieve was contained as a desiccant in the induced organic liquid, only the supernatant induced organic liquid was sampled.

In Examples 1 to 3 in which the second solute is a dehydration reagent, the Karl Fischer reaction and the dehydration reaction compete with each other. Therefore, the water content of the second organic solvent before the addition of the dehydration reagent is induced. It was regarded as the water content of the liquid. The description "moisture content is less than 0.01% by mass" in Examples 1 to 3 means that the water content of the second organic solvent containing no dehydration reagent is 0.01% by mass, and then the dehydration reagent is added. This means that it is presumed that the water content was further reduced.

(Dehydration efficiency)
The dehydration efficiency was determined based on the water content of the raw material liquid (FS) and the amount of the raw material liquid (FS) based on the following formula. In addition, t was set to 30 (minutes).

The value of dehydration efficiency (%) was evaluated according to the following criteria.
A: 40% or more B: 30% or more and less than 40% C: less than 30%

<< Example 1 >>
This example was carried out at room temperature (23 ° C.) using the dehydrator shown in FIG. As the raw material solution, 200 mL of an isopropyl acetate solution containing 10% by mass of octaacetylsucrose, which is the first solute, was used. The initial water content of the raw material liquid was 2.0% by mass. As the induction organic solution, 400 mL of an isopropyl acetate solution containing 10% by mass of triethyl orthoformate as a second solute and a catalytic amount of pyridinium paratoluenesulfonate (PPTS) was used. The initial moisture content of the derived organic solution was less than 0.01% by mass. The raw material liquid tank and the induction liquid tank were covered so that the organic solvent did not move out of the tank due to vaporization. The raw material liquid was circulated at a flow rate of 40 mL / min and the induced organic liquid was circulated at 340 mL / min, respectively, and brought into contact with each other through a forward osmosis membrane. After operating the dehydrator for 4 hours, the water content of the recovered dehydration raw material was 0.6% by mass.

<< Example 2 >>
As the raw material liquid, 200 mL of an ethyl acetate solution containing 10% by mass of octaacetylsucrose, which is the first solute, was used. The initial water content of the raw material liquid was 3.0% by mass. As the induction organic solution, 400 mL of an ethyl acetate solution containing 10% by mass of triethyl orthoformate as a second solute and a catalytic amount of paratoluenesulfonic acid was used. The initial moisture content of the derived organic solution was less than 0.01% by mass. The raw material liquid tank and the induction liquid tank were covered so that the organic solvent did not move out of the tank due to vaporization. After operating the dehydrating apparatus under the same conditions as in Example 1, the water content of the dehydrated raw material liquid recovered was 0.7% by mass.

<< Example 3 >>
As the raw material liquid, 200 mL of a tetrahydrofuran (THF) solution containing 10% by mass of quinine, which is the first solute, was used. The initial water content of the raw material liquid was 9.0% by mass. As the induction solution, 400 mL of a tetrahydrofuran solution containing 10% by mass of triethyl orthoformate as a second solute and a catalytic amount of pyridinium paratoluenesulfonate (PPTS) was used. The initial moisture content of the derived organic solution was less than 0.01% by mass. The raw material liquid tank and the induction liquid tank were covered so that the organic solvent did not move out of the tank due to vaporization. After operating the dehydrator under the same conditions as in Example 1, the water content of the dehydrated raw material recovered was 0.8% by mass.

<< Example 4 >>
As the raw material liquid, 200 mL of a tetrahydrofuran solution containing 10% by mass of quinine as the first solute was used. The initial water content of the raw material liquid was 9.0% by mass. As the inducing solution, 400 mL of a tetrahydrofuran solution containing 10% by mass of toluene as a second solute and about 100 g of molecular sieve as a desiccant was used. The initial water content of the derived organic liquid was 0.01% by mass. The raw material liquid tank and the induction liquid tank were covered so that the organic solvent did not move out of the tank due to vaporization. After operating the dehydrating apparatus under the same conditions as in Example 1, the water content of the dehydrated raw material liquid recovered was 0.9% by mass.

<< Example 5 >>
As the raw material liquid, 200 mL of a tetrahydrofuran solution containing 10% by mass of quinine, which is the first solute, was used. The initial water content of the raw material liquid was 3.0% by mass. As the induction organic liquid, 2000 mL of tetrahydrofuran, which is a second organic solvent, was used. The initial water content of the induced organic liquid was 0.1% by mass. The raw material liquid tank and the induction liquid tank were covered so that the organic solvent did not move out of the tank due to vaporization. After operating the dehydrator for 7 hours under the same conditions as in Example 1, the water content of the recovered dehydration raw material was 0.9% by mass.

<< Example 6 >>
As the raw material solution, 200 mL of an isopropyl acetate solution containing 10% by mass of octaacetylsucrose, which is the first solute, was used. The initial water content of the raw material liquid was 2.0% by mass. As the inducing organic liquid, 600 mL of isopropyl acetate containing about 100 g of molecular sieve, which is a desiccant, was used. The initial water content of the derived organic liquid was 0.01% by mass. In this embodiment, the dehydration operation was performed without covering the raw material liquid tank and the induction liquid tank. After operating the dehydrator for 5 hours under the same conditions as in Example 1, the water content of the recovered dehydration raw material was 0.8% by mass.

<< Comparative Example 1 >>
In Comparative Example 1, an aqueous solution was used as the inducing solution instead of an organic solution. As the raw material liquid, 200 mL of a tetrahydrofuran solution containing 10% by mass of quinine, which is the first solute, was used. The initial water content of the raw material liquid was 9.0% by mass. As the induction liquid, 400 mL of an aqueous solution containing 20% by mass of magnesium chloride, which is the second solute, was used. The raw material liquid tank and the induction liquid tank were covered so that the solvent did not move out of the tank due to vaporization. After operating the dehydrator for 1.5 hours under the same conditions as in Example 1, the water content of the recovered dehydration raw material was measured and found to be 7.2% by mass. Although the water content of the raw material liquid decreased, it could not be less than 1% by mass.

<< Comparative Example 2 >>
In Comparative Example 2, an aqueous solution was used as the inducing solution, as in Comparative Example 1. As the raw material liquid, 200 mL of a tetrahydrofuran solution containing 10% by mass of quinine, which is the first solute, was used. The initial water content of the raw material liquid was 1.3% by mass. As the induction liquid, 400 mL of an aqueous solution containing 20% by mass of magnesium chloride, which is the second solute, was used. The raw material liquid tank and the induction liquid tank were covered so that the solvent did not move out of the tank due to vaporization. After operating the dehydrator for 1.5 hours under the same conditions as in Example 1, the water content of the recovered dehydration raw material was measured and found to be 4.8% by mass. As a result, the water content of the raw material liquid increased, and the raw material liquid could not be dehydrated.

<< Comparative Example 3 >>
In Comparative Example 3, an aqueous solution was used as the inducing solution, as in Comparative Example 1. As the raw material liquid, 200 mL of an ethyl acetate solution containing 10% by mass of octaacetylsucrose, which is the first solute, was used. The initial water content of the raw material liquid was 2.1% by mass. As the induction liquid, 400 mL of an aqueous solution containing 20% by mass of magnesium chloride, which is the second solute, was used. The raw material liquid tank and the induction liquid tank were covered so that the solvent did not move out of the tank due to vaporization. After operating the dehydrator for 1.5 hours under the same conditions as in Example 1, the water content of the recovered dehydration raw material was measured and found to be 2.4% by mass. As a result, the water content of the raw material liquid increased, and the raw material liquid could not be dehydrated.

<< Comparative Example 4 >>
In Comparative Example 4, an aqueous solution was used as the inducing solution, as in Comparative Example 1. As the first organic solvent, methanol that permeates the forward osmosis membrane was selected. As the raw material liquid, 1000 mL of a methanol solution containing 1% by mass of octaacetylsucrose, which is the first solute, was used. The initial water content of the raw material liquid was 10.2% by mass. As the inducing solution, 1600 mL of an aqueous solution containing 10% by mass of magnesium chloride, which is the second solute, was used. The raw material liquid tank and the induction liquid tank were covered so that the solvent did not move out of the tank due to vaporization. After operating the dehydrator for 7 hours under the same conditions as in Example 1, the water content of the recovered dehydration raw material was measured and found to be 38.5% by mass. As a result, the water content of the raw material liquid increased, and the raw material liquid could not be dehydrated.

<< Comparative Example 5 >>
In Comparative Example 5, methanol permeating the forward osmosis membrane was selected as the first organic solvent and the second organic solvent. As the raw material liquid, 900 mL of a methanol solution containing 1% by mass of octaacetylsucrose, which is the first solute, was used. The initial water content of the raw material liquid was 9.4% by mass. As the inducing organic liquid, 1400 mL of a methanol solution containing 10% by mass of magnesium chloride, which is a second solute, was used. The initial water content of the induced organic liquid was 0.13% by mass. The raw material liquid tank and the induction liquid tank were covered so that the organic solvent did not move out of the tank due to vaporization. After operating the dehydrator for 3.5 hours under the same conditions as in Example 1, the water content of the recovered dehydration raw material was measured and found to be 3.0% by mass. Although the water content of the raw material liquid decreased, it could not be less than 1% by mass.

<< Comparative Example 6 >>
In Comparative Example 6, the induced organic liquid was tested under the condition that the initial water content was higher than that of the raw material liquid. As the raw material liquid, 200 mL of a t-butyl methyl ether solution containing 5% by mass of octaacetylsucrose, which is the first solute, was used. The initial water content of the raw material liquid was 1.3% by mass. As the inducing solution, 600 mL of an isopropyl acetate solution containing 10% by mass of toluene, which is the second solute, was used. The initial water content of the induced organic liquid was 1.5% by mass. The raw material liquid tank and the induction liquid tank were covered so that the organic solvent did not move out of the tank due to vaporization. After operating the dehydrator for 1 hour under the same conditions as in Example 1, the water content of the recovered dehydration raw material was measured and found to be 1.4% by mass. As a result, the water content of the raw material liquid increased, and the raw material liquid could not be dehydrated.

<< Example 7 >>
As the raw material liquid, 200 g of a tetrahydrofuran solution containing 0.1% by mass of octaacetylsucrose, which is the first solute, was used. The initial water content of the raw material liquid was 1.1% by mass. As the inducing organic liquid, 400 g of tetrahydrofuran was used. The initial water content of the induced organic liquid was 0.01% by mass. The raw material liquid tank and the induction liquid tank were covered so that the organic solvent did not move out of the tank due to vaporization. After operating the dehydrator for 2 hours under the same conditions as in Example 1, the water content of the recovered dehydration raw material was 0.4% by mass. The dehydration efficiency determined from the water content and weight of the raw material liquid measured after 0 minutes and 30 minutes was 33% (evaluation B).

<< Example 8 >>
As the raw material liquid, 200 g of a tetrahydrofuran solution containing 0.1% by mass of octaacetylsucrose, which is the first solute, was used. The initial water content of the raw material liquid was 1.1% by mass. As the inducing organic liquid, 400 g of ethyl acetate was used. The initial water content of the derived organic liquid was 0.01% by mass. The raw material liquid tank and the induction liquid tank were covered so that the organic solvent did not move out of the tank due to vaporization. After operating the dehydrator for 2 hours under the same conditions as in Example 1, the water content of the recovered dehydration raw material was 0.4% by mass. The dehydration efficiency was 42% (evaluation A) based on the water content and weight of the raw material liquid measured after 0 minutes and 30 minutes.

<< Example 9 >>
As the raw material liquid, 200 g of a tetrahydrofuran solution containing 0.1% by mass of octaacetylsucrose, which is the first solute, was used. The initial water content of the raw material liquid was 1.1% by mass. As the inducing organic liquid, 400 g of methanol was used. The initial water content of the derived organic liquid was 0.01% by mass. The raw material liquid tank and the induction liquid tank were covered so that the organic solvent did not move out of the tank due to vaporization. After operating the dehydrating apparatus for 2 hours under the same conditions as in Example 1, the water content of the recovered dehydrating raw material liquid was 0.5% by mass. The dehydration efficiency was 23% (evaluation C) based on the water content and weight of the raw material liquid measured after 0 minutes and 30 minutes.

<< Example 10 >>
As the raw material liquid, 200 g of a tetrahydrofuran solution containing 0.1% by mass of octaacetylsucrose, which is the first solute, was used. The initial water content of the raw material liquid was 1.1% by mass. As the derived organic liquid, 400 g of a solution in which tetrahydrofuran and cyclohexane were mixed in a volume ratio of 1: 3 was used. The initial water content of the derived organic liquid was 0.01% by mass. The raw material liquid tank and the induction liquid tank were covered so that the organic solvent did not move out of the tank due to vaporization. After operating the dehydrating apparatus for 2 hours under the same conditions as in Example 1, the water content of the recovered dehydrating raw material liquid was 0.9% by mass. The dehydration efficiency was 27% (evaluation C) based on the water content and weight of the raw material liquid measured after 0 minutes and 30 minutes.

<< Example 11 >>
As the raw material liquid, 200 g of a tetrahydrofuran solution containing 0.1% by mass of octaacetylsucrose, which is the first solute, was used. The initial water content of the raw material liquid was 1.1% by mass. As the induction solution, 400 g of a solution in which tetrahydrofuran and cyclohexane were mixed at a volume ratio of 1: 1 was used. The initial water content of the derived organic liquid was 0.01% by mass. The raw material liquid tank and the induction liquid tank were covered so that the organic solvent did not move out of the tank due to vaporization. After operating the dehydrator for 2 hours under the same conditions as in Example 1, the water content of the recovered dehydration raw material was 0.8% by mass. The dehydration efficiency was 39% (evaluation B) based on the water content and weight of the raw material liquid measured after 0 minutes and 30 minutes.

<< Example 12 >>
As the raw material liquid, 200 g of a tetrahydrofuran solution containing 0.1% by mass of octaacetylsucrose, which is the first solute, was used. The initial water content of the raw material liquid was 1.1% by mass. As the inducing solution, 400 g of a solution in which tetrahydrofuran and N-methylpyrrolidone were mixed in a volume ratio of 1: 1 was used. The initial water content of the derived organic liquid was 0.01% by mass. The raw material liquid tank and the induction liquid tank were covered so that the organic solvent did not move out of the tank due to vaporization. After operating the dehydrator for 2 hours under the same conditions as in Example 1, the water content of the recovered dehydration raw material was 0.4% by mass. The dehydration efficiency was 32% (evaluation B) based on the water content and weight of the raw material liquid measured after 0 minutes and 30 minutes.

<< Example 13 >>
As the raw material liquid, 200 g of a tetrahydrofuran solution containing 0.1% by mass of octaacetylsucrose, which is the first solute, was used. The initial water content of the raw material liquid was 1.1% by mass. As the induction solution, 400 g of a solution in which tetrahydrofuran and dichloromethane were mixed in a volume ratio of 1: 1 was used. The initial water content of the induced organic liquid was 0.01% by mass. The raw material liquid tank and the induction liquid tank were covered so that the organic solvent did not move out of the tank due to vaporization. After operating the dehydrator for 2 hours under the same conditions as in Example 1, the water content of the recovered dehydration raw material was 0.5% by mass. The dehydration efficiency was 41% (evaluation A) based on the water content and weight of the raw material liquid measured after 0 minutes and 30 minutes.

<< Example 14 >>
As the raw material liquid, 200 g of a tetrahydrofuran solution containing 0.1% by mass of octaacetylsucrose, which is the first solute, was used. The initial water content of the raw material liquid was 1.1% by mass. As the induction solution, 400 g of a solution in which tetrahydrofuran and dichloromethane were mixed in a volume ratio of 1: 3 was used. The initial water content of the derived organic liquid was 0.01% by mass. The raw material liquid tank and the induction liquid tank were covered so that the organic solvent did not move out of the tank due to vaporization. After operating the dehydrator for 2 hours under the same conditions as in Example 1, the water content of the recovered dehydration raw material was 0.8% by mass. The dehydration efficiency was 38% (evaluation B) based on the water content and weight of the raw material liquid measured after 0 minutes and 30 minutes.

<< Example 15 >>
As the raw material liquid, 200 g of a tetrahydrofuran solution containing 0.1% by mass of octaacetylsucrose, which is the first solute, was used. The initial water content of the raw material liquid was 1.1% by mass. As the induction solution, 400 g of a solution prepared by mixing tetrahydrofuran and dichloromethane in a volume ratio of 1: 9 was used. The initial water content of the induced organic liquid was 0.01% by mass. The raw material liquid tank and the induction liquid tank were covered so that the organic solvent did not move out of the tank due to vaporization. After operating the dehydrator for 2 hours under the same conditions as in Example 1, the water content of the recovered dehydration raw material was 0.9% by mass. The dehydration efficiency was 37% (evaluation B) based on the water content and weight of the raw material liquid measured after 0 minutes and 30 minutes.

The results of the above Examples and Comparative Examples are shown in Tables 2 and 3.

1 Dehydration device 2 Raw material liquid tank 3 Inductive liquid tank 4 Raw material liquid 5 Inductive

organic liquid

6, 7 Raw material liquid feed pipe 8 Raw material

liquid feed pump

9, 10 Inductive liquid feed pipe 11 Inductive liquid feed pump 12 Raw material liquid system 13 Induction liquid system 20 Positive

osmotic membrane module

21, 22 Shell side conduit 23 Positive

permeable membrane

24, 25

Adhesive fixing part

26, 27 Header 28, 29 Core side conduit 30 Housing 41 Hollow thread support film module 42 Core side pressure regulator 43 Shell side pressure regulator 44 Second solution storage tank 45 Second solution liquid feed pipe 46 Second solution liquid feed pump 47 Second solution liquid drain tank 48 Second solution drain pipe 49 End cap S101 Liquid separation process S102 Coarse dehydration Step S103 Dehydration step S104 Regeneration step S105 Crystallization step S106 Water-free reaction step

Claims

A method for dehydrating a raw material solution containing a first organic solvent, water and a first solute.
A dehydration step of bringing the raw material liquid and an induced organic liquid containing a second organic solvent into contact with each other via a forward osmosis membrane to obtain a dehydrated raw material liquid dehydrated to a water content of less than 1% by mass is included.
Here, the initial water content of the raw material liquid in the dehydration step is 1% by mass or more and less than 30% by mass, and the initial water content of the induced organic liquid is smaller than the initial water content of the raw material liquid. Method.
The forward osmosis membrane is a composite membrane composed of a separation active layer and a microporous support membrane.
The difference ΔHSP of the solubility parameter between the induced organic liquid and the separated active layer is ΔHSP <16 (MPa) 0.5 , and the saturated water content of the induced organic liquid is 0.5% by mass or more.
The method according to claim 1.
The solubility parameter of the derived organic liquid is 13 (MPa) 0.5 ≤ δd ≤ 20 (MPa) 0.5 , 2 (MPa) 0.5 ≤ δp ≤ 18 (MPa) 0.5 , 2 (MPa) 0.5 ≤ δH ≤ 28 (MPa) 0.5 . Is,
The method according to claim 1 or 2.
The derived organic liquid further comprises a second solute and / or desiccant.
The method according to any one of claims 1 to 3.
The dehydration step is performed in a dehydrating apparatus including a raw material liquid system for circulating the raw material liquid and an induction liquid system for circulating the inductive organic liquid.
The raw material liquid system and the induction liquid system are configured to suppress the movement of the first organic solvent and the second organic solvent to the outside of the system due to vaporization.
The method according to any one of claims 1 to 4.
The second organic solvent is tetrahydrofuran, 2-methyl tetrahydrofuran, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, toluene, cyclopentyl methyl ether, t-butyl methyl ether, acetonitrile, dimethylacetamide, N-methylpyrrolidone, hexafluoroisopropyl alcohol, acetic acid, acetone, anisole, benzene, chlorobenzene, carbon tetrachloride, chloroform, cumene, cyclohexane, 1,2-dichloroethane, 1,2-dichloroethane, dichloromethane, 1,2-dimethoxy Ethan, N, N-dimethylformamide, dimethylsulfoxide, 1,4-dioxane, ethyl ether, ethyl formate, formamide, formate, heptane, hexane, methylbutylketone, methylcyclohexane, methylethylketone, methylisobutylketone, pentane, nitromethane, pyridine , Sulfolane, tetralin, 1,1,1-trichloroethane, 1,1,2-trichloroethane, and xylene, at least one selected from the group.
The method according to any one of claims 1 to 5.
In the dehydration step, an organic liquid containing the first organic solvent and having a water content of 0.5% by mass or less is replenished with the raw material liquid whose volume has been reduced by dehydration and concentration.
The method according to any one of claims 1 to 6.
The first solute in the dehydration raw material liquid is subjected to a water-free reaction in which the first solute is chemically reacted with other reagents under anhydrous conditions.
The method according to any one of claims 1 to 7.
The method further comprises a crystallization step of purifying the first solute by crystallization.
The method according to any one of claims 1 to 8.
The method further comprises a liquid separation step of extracting the organic layer from the liquid containing the first solute prior to the dehydration step.
The organic layer is used as the raw material liquid.
The method according to any one of claims 1 to 9.
The method further comprises a regeneration step.
The regeneration step is a step of removing water transferred from the raw material liquid to the derived organic liquid from the derived organic liquid.
The method according to any one of claims 1 to 10.
In the regeneration step, a desiccant or a dehydrating reagent is added to the induced organic liquid.
11. The method of claim 11.
In the regeneration step, the induced organic liquid is dehydrated by azeotropic distillation or membrane treatment.
The method according to claim 11 or 12.
The method further comprises a crude dehydration step prior to the dehydration step.
In the crude dehydration step, the crude raw material solution and the induced aqueous solution containing the third solute are brought into contact with each other via a forward osmosis membrane to dehydrate the raw material solution to a moisture content of 1% by mass or more and less than 30% by mass. The process of getting
The method according to any one of claims 1 to 13.
The crude dehydration step is performed in a dehydrator including a raw material liquid system for circulating the crude raw material liquid and an induction liquid system for circulating the inductive aqueous solution.
The raw material liquid system is configured to suppress the movement of the first organic solvent to the outside of the system due to vaporization.
14. The method of claim 14.
In the crude dehydration step, an organic liquid containing the first organic solvent and having a water content of 0.5% by mass or less is replenished with the crude raw material liquid whose volume has been reduced by dehydration and concentration.
The method of claim 14 or 15.
The method according to any one of claims 1 to 16, wherein the method is used in the manufacture of a pharmaceutical product.